Strong Electronic Coupling Research Articles

Graphite conjugated nickel phthalocyanine for efficient CO2 electroreduction and Zn-CO2 batteries.

The linking chemistry between molecular catalysts and substrates is a crucial challenge for enhancing electrocatalytic performance. Herein, we elucidate the influence of various immobilization methods of amino-substituted Ni phthalocyanine catalysts on their electrocatalytic CO2 reduction reaction (eCO2RR) activity. A graphite-conjugated Ni phthalocyanine, Ni(NH2)8Pc-GC, demonstrates remarkable electrocatalytic performance both in H-type and flow cells. In situ infrared spectroscopy and theoretical calculations reveal that the graphite conjugation, through strong electronic coupling, increases the electron density of the active site, reduces the adsorption energy barrier of *COOH, and enhances the catalytic performance. As the cathode catalyst, Ni(NH2)8Pc-GC also displays remarkable charge-discharge cycle stability of over 50 hours in a Zn-CO2 battery. These findings underscore the significance of immobilization methods and highlight the potential for further advancements in eCO2RR.

Component-controlled synthesis of PdxSny nanocrystals on carbon nanotubes as advanced electrocatalysts for oxygen reduction reaction.

Pd-based bimetallic or multimetallic nanocrystals are considered to be potential electrocatalysts for cathodic oxygen reduction reaction (ORR) in fuel cells. Although much advance has been made, the synthesis of component-controlled Pd-Sn alloy nanocrystals or corresponding nanohybrids is still challenging, and the electrocatalytic ORR properties are not fully explored. Herein, component-controlled synthesis of PdxSny nanocrystals (including Pd3Sn, Pd2Sn, Pd3Sn2, and PdSn) has been realized, which are in situ grown or deposited on pre-treated multi-walled carbon nanotubes (CNTs) to form well-coupled nanohybrids (NHs) by a facile one-pot non-hydrolytic system thermolysis method. In alkaline media, all the resultant PdxSny/CNTs NHs are effective at catalyzing ORR. Among them, the Pd3Sn/CNTs NHs exhibit the best catalytic activity with the half-wave potential of 0.85 V (vs. RHE), good cyclic stability, and excellent methanol-tolerant capability due to the suited Pd-Sn alloy component and its strong interaction or efficient electronic coupling with CNTs. This work is conducive to the advancement of Pd-based nanoalloy catalysts by combining component engineering and a hybridization strategy and promoting their application in clean energy devices.

Computational approaches to enhance charge transfer and stability in TPBi-(PEA)2PbI4 perovskite interfaces through molecular orientation optimization.

The optimization of material interfaces is crucial for the performance and longevity of optoelectronic devices. This study focuses on 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), a key component in perovskite devices known for its efficient charge transfer capabilities. We investigate the TPBi-(PEA)2PbI4 heterostructure interfaces to enhance device durability by optimizing interfacial properties. Our findings reveal that those specific TPBi orientations - at 15 and 30 degrees - ensure strong electronic coupling between TPBi and (PEA)2PbI4, which improves stability at these interfaces. Furthermore, orientations at 15 and 60 degrees markedly enhance charge transfer kinetics, indicating reduced recombination rates and potentially increased efficiency in optoelectronic devices. These results not only underscore the importance of molecular orientation in perovskite devices but also open new avenues for developing more stable and efficient hybrid materials in optoelectronic applications.

Deciphering the doublet luminescence mechanism in neutral organic radicals: spin-exchange coupling, reversed-quartet mechanism, excited-state dynamics.

Neutral organic radical molecules have recently attracted considerable attention as promising luminescent and quantum-information materials. However, the presence of a radical often shortens their excited-state lifetime and results in fluorescence quenching due to enhanced intersystem crossing (EISC). Recently, an experimental report introduced an efficient luminescent radical molecule, tris(2,4,6-trichlorophenyl)methyl-carbazole-anthracene (TTM-1Cz-An). In this study, we systematically performed quantum theoretical calculations combined with the path integral approach to quantitatively calculate the excited-state dynamics processes and spectral characteristics. Our theoretical findings suggest that the sing-doublet D1 state, originating from the anthracene excited singlet state, is quickly converted to the doublet (trip-doublet) state via EISC, facilitated by a significant nonequivalence exchange interaction, with ΔJ ST = 0.174 cm-1. The formation of the quartet state (Q1, trip-quartet) was predominantly dependent on the exchange coupling 3/2J TR = 0.086 cm-1 between the triplet spin electrons of anthracene and the TTM-1Cz radical. Direct spin-orbit coupling ISC to the Q1 state was minimal due to the nearly identical spatial wavefunctions of the and Q1 levels. The effective occurrence of reverse intersystem crossing (RISC) from the Q1 to D1 state is a critical step in controlling the luminescence of TTM-1Cz-An. The calculated RISC rate k RISC, including the Herzberg-Teller effect, was 3.64 × 105 s-1 at 298 K, significantly exceeding the phosphorescence and nonradiative rates of the Q1 state, thus enabling the D1 repopulation. Subsequently, a strong electronic coupling of 37.4 meV was observed between the D1 and D2 states, along with a dense manifold of doublet states near the D1 state energy, resulting in a larger reverse internal conversion rate k RIC of 9.26 × 1010 s-1. Distributed to the D2 state, the obtained emission rate of k f = 2.98-3.18 × 107 s-1 was in quite good agreement with the experimental value of 1.28 × 107 s-1, and its temperature effect was not remarkable. Our study not only provides strong support for the experimental findings but also offers valuable insights for the molecular design of high-efficiency radical emitters.

Sr-Stabilized IrMnO2 Solid Solution Nano-Electrocatalysts with Superior Activity and Excellent Durability for Oxygen Evolution Reaction in Acid Media.

The development of cost-effective catalysts for oxygen evolution reaction (OER) in acidic media is of paramount importance. This work reports that Sr-doped solid solution structural ultrafine IrMnO2 nanoparticles (NPs) (≈1.56nm) on the carbon nanotubes(Sr-IrMnO2/CNTs) are efficient catalysts for the acidic OER. Even with the Ir use dosage 3.5 times lower than that of the commercial IrO2, the Sr-IrMnO2/CNTs only need an overpotential of 236.0mV to drive 10.0mA cm-2 and show outstanding stability for >400.0 h. Its Ir mass activity is 39.6 times higher than that of the IrO2 at 1.53V. The solid solution and Sr-doping structure of Sr-IrMnO2 are the main origin of the high catalytic activity and excellent stability of the Sr-IrMnO2/CNTs. The density function theory calculations indicate that the solid solution structure can promote strong electronic coupling between Ir and Mn, lowering the energy barrier of the OER rate-determining step. The Sr-doping can enhance the stability of Ir against the chemical corrosion and demetallation. Water electrolyzers and proton exchange membrane water electrolyzers assembled with the Sr-IrMnO2/CNTs show superb performance and excellent durability in the acid media.

Tryptophan to Tryptophan Hole Hopping in an Azurin Construct.

Electron transfer (ET) between neutral and cationic tryptophan residues in the azurin construct [ReI(H126)(CO)3(dmp)](W124)(W122)CuI (dmp = 4,7-Me2-1,10-phenanthroline) was investigated by Born-Oppenheimer quantum-mechanics/molecular mechanics/molecular dynamics (QM/MM/MD) simulations. We focused on W124•+ ← W122 ET, which is the middle step of the photochemical hole-hopping process *ReII(CO)3(dmp•-) ← W124 ← W122 ← CuI, where sequential hopping amounts to nearly 10,000-fold acceleration over single-step tunneling (ACS Cent. Sci. 2019, 5, 192-200). In accordance with experiments, UKS-DFT QM/MM/MD simulations identified forward and reverse steps of W124•+ ↔ W122 ET equilibrium, as well as back ET ReI(CO)3(dmp•-) → W124•+ that restores *ReII(CO)3(dmp•-). Strong electronic coupling between the two indoles (≥40 meV in the crossing region) makes the productive W124•+ ← W122 ET adiabatic. Energies of the two redox states are driven to degeneracy by fluctuations of the electrostatic potential at the two indoles, mainly caused by water solvation, with contributions from the protein dynamics in the W122 vicinity. ET probability depends on the orientation of Re(CO)3(dmp) relative to W124 and its rotation diminishes the hopping yield. Comparison with hole hopping in natural systems reveals structural and dynamics factors that are important for designing efficient hole-hopping processes.

Confinement Engineering of Zinc Single-Atom Triggered Charge Redistribution on Ruthenium Site for Alkaline Hydrogen Production.

Optimizing the interaction between metal and support in the supported metal catalysts effectively refines the electronic structure and boosts the catalytic properties of loaded active components. Herein a method is introduced to confine ultrafine ruthenium (Ru) nanoparticles within atomically dispersed Zn-N4 sites on a N-doped carbon network (Ru/Zn-N-C) through the strong electronic metal-support interaction, achieving superior catalytic activity and stability for alkaline hydrogen evolution. Spectroscopic data and theoretical modeling elucidate that the remarkable catalytic performance of Ru sites stems from their strong electronic coupling with neighboring Zn-N4 moiety and pyridinic N/pyrrolic N. This interaction induces an electron-deficient state of Ru, thereby accelerating the dissociation of H2 O and lowering the energy barriers for the desorption of OH* and H*. This insight provides a deeper understanding of the catalytic mechanisms at play. Furthermore, alkaline water electrolyzer using this catalyst as cathode delivers a mass activity of 3Amgcat -1 at 2.0V, much surpassing Ru-C. This research opens a novel pathway for the development of advanced materials , tailored for energy storage and conversion applications.

Coupled cluster cavity Born-Oppenheimer approximation for electronic strong coupling.

Chemical and photochemical reactivity, as well as supramolecular organization and several other molecular properties, can be modified by strong interactions between light and matter. Theoretical studies of these phenomena require the separation of the Schrödinger equation into different degrees of freedom as in the Born-Oppenheimer approximation. In this paper, we analyze the electron-photon Hamiltonian within the cavity Born-Oppenheimer approximation (CBOA), where the electronic problem is solved for fixed nuclear positions and photonic parameters. In particular, we focus on intermolecular interactions in representative dimer complexes. The CBOA potential energy surfaces are compared with those obtained using a polaritonic approach, where the photonic and electronic degrees of freedom are treated at the same level. This allows us to assess the role of electron-photon correlation and the accuracy of CBOA.

Thickness-Dependent Charge Transport in Three Dimensional Ru(II)- Tris(phenanthroline)-Based Molecular Assemblies.

We describe here the fabrication of large-area molecular junctions with a configuration of ITO/[Ru(Phen)3]/Al to understand temperature- and thickness-dependent charge transport phenomena. Thanks to the electrochemical technique, thin layers of electroactive ruthenium(II)-tris(phenanthroline) [Ru(Phen)3] with thicknesses of 4-16 nm are covalently grown on sputtering-deposited patterned ITO electrodes. The bias-induced molecular junctions exhibit symmetric current-voltage (j-V) curves, demonstrating highly efficient long-range charge transport and weak attenuation with increased molecular film thickness (β = 0.70 to 0.79 nm-1). Such a lower β value is attributed to the accessibility of Ru(Phen)3 molecular conduction channels to Fermi levels of both the electrodes and a strong electronic coupling at ITO-molecules interfaces. The thinner junctions (d = 3.9 nm) follow charge transport via resonant tunneling, while the thicker junctions (d = 10-16 nm) follow thermally activated (activation energy, Ea ∼ 43 meV) Poole-Frenkel charge conduction, showing a clear "molecular signature" in the nanometric junctions.

Enhanced dry reforming of methane over NixCoy-HAP catalysts: Insights into the effect of Co species on carbon deposition and RWGS

Co and Ni are widely used to prepare bimetallic catalysts for dry reforming of methane (DRM) due to their comparable electronic configurations. In this study, a series of NixCoy-HAP catalysts were prepared, and by combining the characterization with XRD, H2-TPR, XPS, and TEM, the influence of Co incorporation on the redox properties, catalytic activity, catalytic stability, carbon deposition resistance and side reactions of the catalysts was evaluated. The results showed that both Ni and Co are homogeneously dispersed in the HAP structure by ion-exchange. The addition of Co enhances the reducibility of NixCoy-HAP and significantly improves the catalytic activity in the initial stage. Ni5Co1-HAP exhibits best catalytic stability in a 100-h long-term reaction accompanied by the deactivation of CH4 and CO2 with only 0.09% h−1 and 0.10% h−1, respectively. Characterization of the spent catalysts demonstrates that the decrease in activity of high Co content catalysts (Ni1Co5-HAP and Ni1Co10-HAP) is not due to carbon deposition, but rather that the addition of Co facilitates the RWGS side reaction. Process characterization of the catalysts in the CH4 one-component reaction indicates that an increase in the concentrates of one promotes a faster reduction of the other metal due to the strong electronic coupling of Ni and Co. These insights revealed here can pave the way for the preparation of Ni–Co bimetallic catalysts with high catalytic activity, robust resistance to carbon deposition and inhibition of a RWGS side reaction.

Tailoring the Chemisorption Manner of Fe d‐Band Center with La2O3 for Enhanced Oxygen Reduction in Anion Exchange Membrane Fuel Cells

AbstractEngineering the electronic configuration and intermediates adsorption behaviors of high‐performance non‐noble‐metal‐based catalysts for the sluggish oxygen reduction reaction (ORR) kinetics at the cathode is highly imperative for the development of anion exchange membrane fuel cells (AEMFCs), yet remains an enormous challenge. Herein, a rare‐earth metal oxide engineering tactic through the formation of Fe3O4/La2O3 heterostructures in N,O‐doped carbon nanospheres (Fe3O4/La2O3@N,O‐CNSs) for efficient oxygen reduction electrocatalysis is reported. The theoretical calculations reveal that the interfacial bonds formed by the La─O─Fe heterogeneous interface effectively optimize the electronic structure of the Fe d‐band center relative to the Fermi level, which results in a significant reduction of the reaction barriers of rate‐limiting steps during the ORR. The modulation in intermediates chemisorption enables Fe3O4/La2O3@N,O‐CNSs an outstanding ORR performance and improved stability, with a significantly higher half‐wave potential value (0.88 V). More impressively, this integrated catalyst delivers a remarkable power density of 148.7 mW cm−2 in practical AEMFC operating conditions, along with negligible performance degradation over 100 h using an H2‐air atmosphere, which is higher than commercial Pt/C‐coupled electrodes. The results presented here are believed to provide guidelines for fabricating high‐performance AEMFCs electrocatalysts in terms of heterointerface engineering and strong electronic coupling effect induced by rare‐earth oxides.

Constructing stable V2O5/V6O13 heterostructure interface with fast Zn2+ diffusion kinetics for ultralong lifespan zinc‐ion batteries

Given their plentiful reserves, impressive safety features, and economical pricing, aqueous zinc − ion batteries (ZIBs) have positioned themselves as strong competitors to lithium − ion batteries. Yet, the scarcity of available cathode materials poses a challenge to their continued development. In this study, a V2O5/V6O13 heterostructure has been synthesized using a one − pot hydrothermal approach and employed as the cathode material for ZIBs. As evidenced by both experimental and theoretical findings, V2O5/V6O13 heterostructure delivers a rapid electrons and ions diffusion kinetics promoted by the stable interface and strong electronic coupling with significant charge transfer between V2O5 and V6O13, as well as a stable interface achieved by adjusting V − O bond length. Consequently, the optimized V2O5/V6O13 heterostructure cathode of ZIBs demonstrates exceptional capacity (338 mAh g−1 at 0.1 A g−1), remarkable cycling stability (92.96 % retained after 1400 cycles at 1 A g−1). Through comprehensive theoretical calculations and ex situ characterization, the kinetic analysis and storage mechanism of Zn2+ are thoroughly investigated, providing a solid theoretical foundation for the advancement of novel V − based cathode materials aimed at enhancing the performance of ZIBs.

Strong electron coupling of FeP4/Ni2P to boost highly-efficient electrochemical nitrate reduction to ammonia

Electrochemical reduction of contaminated nitrate to ammonia (NRA) opens a new window for mass production of ammonia and the alleviation of energy crises and environmental pollution. However, fabricating effective catalysts for the NRA still faces significant challenges. Herein, a highly-efficient NRA catalyst, FeP4/Ni2P, was successfully constructed. The strong electron coupling at heterointerfaces of FeP4/Ni2P promoted the generation of abundant active hydrogen *H, inhibited the competition of the HER, accelerated the hydrogenation of the NRA. Benefiting from these, the catalyst displays good NRA catalytic activity in the neutral electrolyte, with the NH3 FE of 97.83 ± 0.091 %, NH3 selectivity of 98.67 ± 0.50 %, NH3 yield rate of 0.262 ± 0.01 mmol·h−1·cm−2, and NO3– conversion rate of 93.02 ± 0.14 %. The DFT theoretical calculations demonstrated that the FeP4/Ni2P heterointerfaces played a critical role in shearing the H-OH bonds of water, resulting in generating more active hydrogen as a key NRA hydrogenation source, and hindering the *H dimerization to form H2, enhancing the NH3 selectivity. This work has a certain reference value for designing excellent catalysts for the NRA.

Enhanced copper anticorrosion from Janus-doped bilayer graphene

The atomic-thick anticorrosion coating for copper (Cu) electrodes is essential for the miniaturisation in the semiconductor industry. Graphene has long been expected to be the ultimate anticorrosion material, however, its real anticorrosion performance is still under great controversy. Specifically, strong electronic couplings can limit the interfacial diffusion of corrosive molecules, whereas they can also promote the surficial galvanic corrosion. Here, we report the enhanced anticorrosion for Cu simply via a bilayer graphene coating, which provides protection for more than 5 years at room temperature and 1000 h at 200 °C. Such excellent anticorrosion is attributed to a nontrivial Janus-doping effect in bilayer graphene, where the heavily doped bottom layer forms a strong interaction with Cu to limit the interfacial diffusion, while the nearly charge neutral top layer behaves inertly to alleviate the galvanic corrosion. Our study will likely expand the application scenarios of Cu under various extreme operating conditions.

Interfacial interaction promoted titanium oxide-based organic-inorganic nanoheterojunctions by chiral host-guest binding

Although titanium oxide (TiO2)-based organic-inorganic nanostructures attract increasing attention in energy fields, accurate regulation of close contact between TiO2 and organic components in nanostructures that determines their performance is still a critical task. Here, the interfacial interaction in TiO2-based organic-inorganic nanoheterojunctions is promoted by host-guest interactions, which are obtained through chiral recognition between chirality imprinted TiO2 and chiral organic molecules (L-PheAD), leading to their close contact. This close contact is due to the matching structure obtained from a multi-level chirality transfer between TiO2 and L-PheAD during molecular imprinting, facilitating the strong electronic coupling and resulting in a positive correlation between chiral signal intensity and the interface bonding strength in the nanoheterojunction. The tightly packed interface is further confirmed by the enhanced photocatalytic activity of TiO2-L-PheAD nanoheterojunctions. This work creates an opportunity to tailor the intimate contact between organic-inorganic interfaces based on host-guest systems with matched chiral space.

Amorphous Ni-Fe-Mo Oxides Coupled with Crystalline Metallic Domains for Enhanced Electrocatalytic Oxygen Evolution by Promoted Lattice-Oxygen Participation.

The crystalline/amorphous heterophase nanostructures are promising functional materials for biomedicals, catalysis, energy conversion, and storage. Despite great progress is achieved, facile synthesis of crystalline metal/amorphous multinary metal oxides nanohybrids remains challenging, and their electrocatalytic oxygen evolution reaction (OER) performance along with the catalytic mechanism are not systematically investigated. Herein, two kinds of ultrafine crystalline metal domains coupled with amorphous Ni-Fe-Mo oxides heterophase nanohybrids, including Ni/Ni0.5-a Fe0.5 Mo1.5 Ox and Ni-FeNi3 /Ni0.5-b Fe0.5-y Mo1.5 Ox , are fabricated through controllable reduction of amorphous Ni0.5 Fe0.5 Mo1.5 Ox precursors by simply tuning the amount of used reductant. Due to the suited component in metal domains, the special structure with dense crystalline/amorphous interfaces, and strong electronic coupling of their components, the resultant Ni-FeNi3 /Ni0.5-b Fe0.5-y Mo1.5 Ox nanohybrids show greatly enhanced OER activity with a low overpotential (278mV) to reach 10mAcm-2 current density and ultrahigh turnover frequency (38160h-1 ), outperforming Ni/Ni0.5-a Fe0.5 Mo1.5 Ox , Ni0.5 Fe0.5 Mo1.5 Ox precursors, commercial IrO2 , and most of recently reported OER catalysts. Also, such Ni-FeNi3 /Ni0.5-b Fe0.5-y Mo1.5 Ox nanohybrids manifest good catalytic stability. As revealed by a series of spectroscopy and electrochemical analyses, their OER mechanism follows the lattice-oxygen-mediated (LOM) pathway. This work may shed light on the design of advanced heterophase nanohybrids, and promote their applications in water splitting, metal-air batteries, or other clean energy fields.

MoO2/Ni heterojunction with strong electronic coupling prepared by in-situ phase separation for High-Efficiency nitrate electroreduction to ammonia

Further improvements in ammonia selectivity and Faraday efficiency are severely hampered by the complexity of the nitrate reduction process and the intense competitive reaction. Therefore, it is awfully imperative to develop highly active NITRR electrocatalysts and further investigate their catalytic mechanism. In this work, MoO2/Ni cuboids with intimate interfaces were constructed by in-situ phase separation induced strategy for electrocatalytic reduction of nitrate and selective synthesis of ammonia, further expanding the application field of this metallic oxide-metal heterostructure catalyst. The experimental results indicate that the strong interaction between MoO2 and Ni causes the redistribution of interfacial charges, which reasonably explains the extraordinary NITRR activity of MoO2/Ni. In addition, the exposure of numerous active sites at the interface and the amelioration of inherent conductivity are also advantageous for the enhancement of catalytic activity. The theoretical results elucidate the detailed catalytic mechanism. MoO2/Ni showcases lower·NH3 desorption energy and higher hydrogen adsorption energy than pure MoO2 and Ni, which promotes the production of ammonia. In short, the strong electronic interaction between MoO2 and Ni tailors the electronic structure of MoO2/Ni, thus regulating the adsorption energy of the intermediates, and observably improving the FE (95.9%) and ammonia selectivity (96.9%) of MoO2/Ni.

Ab initio methods for polariton chemistry

Polariton chemistry exploits the strong interaction between quantized excitations in molecules and quantized photon states in optical cavities to affect chemical reactivity. Molecular polaritons have been experimentally realized by the coupling of electronic, vibrational, and rovibrational transitions to photon modes, which has spurred a tremendous theoretical effort to model and explain how polariton formation can influence chemistry. This tutorial review focuses on computational approaches for the electronic strong coupling problem through the combination of familiar techniques from ab initio electronic structure theory and cavity quantum electrodynamics, toward the goal of supplying predictive theories for polariton chemistry. Our aim is to emphasize the relevant theoretical details with enough clarity for newcomers to the field to follow, and to present simple and practical code examples to catalyze further development work.

Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries

The application of Li–O2 batteries (LOBs) with ultra-high theoretical energy density is limited due to the slow redox kinetics and serious side reactions, especially in high-rate cycles. Herein, CeO2 is constructed on the surface of Mn2O3 through an interface engineering strategy, and Mn2O3@CeO2 heterojunction with good activity and stability at high current density is prepared. The interfacial properties of catalyst and formation mechanism of Li2O2 are deeply studied by density functional theory (DFT) and experiments, revealing the charge-discharge reaction mechanism of LOBs. The results show that the strong electron coupling between Mn2O3 and CeO2 can promote the formation of oxygen vacancies. Heterojunction combined with oxygen vacancy can improve the affinity for O2 and LiO2 reaction intermediates, inducing the formation of thin-film Li2O2 with low potential and easy decomposition, thus improving the cycle stability at high current density. Consequently, it achieved a high specific capacity of 12545 at 1000 mA g−1 and good cyclability of 120 cycles at 4000 mA g−1. This work thus sheds light on designing efficient and stable catalysts for LOBs under high current density.

High catalytic activity of amorphous/crystalline heterostructures in Au nanoparticles: A theoretical investigation

The exploration of highly active and stable catalysts for hydrogen evolution reaction (HER) is the promising solution to the energy crisis, with increasing energy consumption and growing concern about environmental pollution. Recently, amorphous/crystalline (a/c) heterostructures have enabled the catalytic properties to be significantly enhanced due to the strong interfacial electron coupling, realizing the deep optimization of catalytic activity. However, the mechanism of the microscopic catalysis between the active sites and the surrounding ligand is not sufficiently clarified for a/c heterostructure catalysts. Here, Au nanoparticles (AuNPs) with core-shell a/c heterogeneously bound are rationally constructed, whereby the structure-reactivity relationship of AuNPs in the catalytic process and their electronic properties at the surface-active site are thoroughly inspected utilizing molecular dynamics and density-functional tight-binding. As the temperature increases, the size effect of 4 nm AuNPs gradually masks their electronic effect. And the formation free energy of H* reaches the highest catalytic performance of －0.41 eV at 900 K. The introduction of the amorphous phase makes it possible to increase the proportion of active sites with nine coordination numbers from 1 % to 22 %, decreasing the energy barrier of the reaction intermediate and increasing the catalytic activity. Furthermore, the synergy between the amorphous and crystalline phases lowers the d-band center due to the extension of the amorphization, and reaches the maximum change at 900 K, reducing the d-band center of the HER from －0.40 eV (0 K) to －0.48 eV. This investigation delivers explicit insights into the action of a/c heterostructures in optimizing catalytic activity and explores innovative ideas for devising efficient and stable nanoparticle catalysts.